Amino-functional silane compounds

ABSTRACT

A silicone compound of the formula, WHERE L is selected from secondary amine groups and R10 groups, R1 and R2 are selected from hydrocarbon groups and R3 and R4 are selected from hydrogen, hydrocarbon groups and other amine groups. Further, n is a whole number that varies from 1 to 20 and a is a whole number that varies from 0 to 2. These aminofunctional silane compounds may be used as sewage flocculents.

United States Patent Berger et al.

AMINO-FUNCTIONAL SILANE COMPOUNDS Inventors: Abe Berger; Terry G. Selln,both of Schenectady, NY.

Assignee: General Electric Company Filed: Aug. 12, 1971 Appl. No.:171,337

U.S. Cl ..260/448.2 N, 210/54, 252/357, 260/239 E, 260/4482 B, 260/4482E, 260/448.8 R

Int. Cl. ..C07f 7/10, C07f 7/ 18 Field of Search...260/448.2 N, 448.8 R,448.2 E

References Cited UNITED STATES PATENTS 9/1965 Gilkey et al.....260/448.8 R X 4/ 1969 Sam ..260/448.2 N

8/ 1971 Robinson et X 8/ 1971 Berger ..260/448.2 E

Primary Examiner-Tobias E. Levow Assistant Examiner-P. F. ShaverAttorney-Donald J. Voss et al.

[ ABSTRACT A silicone compound of the formula,

R. o R2 R R3 as [wmhpatatatwl where L is selected from secondary aminegroups and R 0 groups, R and R are selected from hydrocarbon groups andR and R are selected from hydrogen, hydrocarbon groups and other aminegroups. Further, n is a whole number that varies from 1 to 20 and a is awhole number that varies from 0 to 2. These aminofunctional silanecompounds may be used as sewage flocculents.

7 Claims, No Drawings AMINO-FUNCTIONAL SILANE COMPOUNDS BACKGROUND OFTHE INVENTION The present invention relates to silicone compounds and,in particular, the present invention relates to silicone compoundshaving an amine-functional group thereon and further, where the compoundis produced from an acrylate intermediate.

Flocculating agents for precipitating colloidal particles from varioustypes of suspensions are well known in the art. In particular, at thepresent time there has been a great deal of research carried out in thedevelopment of waste water treatment and particularly organic or sewagewaste water treatment. During this treatment, organic waste matter inthe form of colloidal particles become suspended in the waste watersystem and during the processing of this waste water it becomesnecessary to flocculate and precipitate the organic colloidal particles.It has been found that some of the more efficient flocculating agentsfor precipitating such colloidal organic matter from waste water are thecationic polyelectrolytes. It is, of course, appreciated that theefiiciency of the various cationic polyelectrolytes vary and thus thereis a constant search for more efficient cationic electrolytes forflocculating organic colloidal matter.

It has been noticed that a combination of a silica sol with certainsilanes will produce a very efficient flocculating agent for organiccolloidal matter. In this respect, there is constant research anddevelopment of silanes and silicone compounds that will co-react withsilica sol and other systems, as well as operate by themselves asefficient flocculating agents for organic colloidal matter.

In addition, bonding agents and, in particular, bonding agents fordifferent types of resins and plastics to glass, glass fibers and othersuch types of glass materials are constantly being sought after. Inparticular, since glass fibers are so widely used for the production ofvarious articles, there is a constant search for the development ofbetter bonding agents for bonding olefinically functional plastics andresins to glass fibers. To produce such a bonding agent, it is necessarythat the compound have a group that will be reactive with the glassfibers, silica and other types of glass and also have a reactive groupthat will be reactive with the plastic resin. The more reactive thegroup on the bonding compound is towards the plastic resin, the firmerand stronger the bond that will be formed by the bonding agent.

Thus, it is one object of the present invention to provide a new classof silicone compounds.

It is another object of the present invention to provide a novel processfor producing a novel class of silicone compounds.

it is yet another object of the present invention to provide a novelflocculating agent for organic colloidal matter.

It is still another object of the present invention to provide a novelclass of silicone compounds for bonding various resins to glass fibersand other types of silica material.

These and other objects of the present invention are accomplished bymeans of the invention defined below.

SUMMARY OF THE INVENTION In accordance with the present invention, thereis provided a silicone compound of the formula,

where L is selected from the group consisting of R' N- and R'0-, R and Rare selected from the class consisting of monovalent hydrocarbonradicals and monovalent halogenated hydrocarbon radicals, R is selectedfrom the class consisting of alkyl, hydrogen and aryl radicals of up to10 carbon atoms, R and R are independently selected from the classconsisting of hydrogen, aryl radicals, alkyl radicals,

R OR, where R is a divalent hydrocarbon radical selected from the classconsisting of alkylene and arylene radicals of up to 10 carbon atoms, nis a whole number that varies from 1 to 20 and a is a whole number thatvaries from O to 2.

In the formula, preferably R, R and R are methyl and n is equal to 3.Further, preferably a is equal to 0.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In formula (I), theradicals R and R may be, for example, alkyl radicals, e.g., methyl,ethyl, propyl, butyl, octyl, etc. radicals; aryl radicals, e.g., phenyl,naphthyl, tolyl, xylyl, etc. radicals; aralkyl radicals, e.g., benzyl,phenylethyl, etc. radicals; alkenyl radicals, e.g., vinyl, allyl,cyclohexenyl, etc. radicals; cycloalkyl radicals, e.g., cyclohexyl,cycloheptyl, etc. radicals; halogensubstituted monovalent hydrocarbonradicals such as, for example, chloromethyl, chloroethyl,dibrom'ophenyl, etc. radicals, and other such types of radicals.Preferably, the radicals R and R have no more than 10 carbon atoms and,more preferably, have no more than six carbon atoms. Preferably, R ismethyl and R is methyl or ethyl. As stated previously, a is a wholenumber that varies from 0 to 2, but is more preferably 0. The symbol nis a whole number that varies from 1 to 20 and is preferably 1 to 10,such as methylene, ethylene, trimethylene, etc. The radicals R areindependently selected, that is, one R radical may be different from theother R radical. These R radicals are independently selected from alkyland aryl radicals of up to 10 carbon atoms, such as methyl, ethyl,propyl, butyl, etc. The radicals R and R may be hydrogen, alkylradicals, cycloalkyl radicals, aryl radicals of up to 15 carbon atoms.The radical R is a divalent hydrocarbon radical selected from alkyleneand arylene radicals of up to 10 carbon atoms, such as methylene,ethylene, phenylene, etc.

The preferred compound is that having the formula,

0 CH H CH ll was ;a;weessarpraia ie mksflt l a H JaHg,

(H) CH3 CH2 The silane of formula (1) is produced by reacting a silanehaving the formula,

R, R2 R2 3'a l 2)n with a compound of the formula,

R3 n -q rn The symbols and radicals L, R, R R R R, n and a are aspreviously defined. The compounds of formula (2) and formula (3) aboveare preferably reacted in a stoichiometric relationship. It is notnecessary that the reaction take place in the presence of a solvent.However, one of the common inert hydrocarbon solvents or ether may beused as a solvent in this reaction. Such solvents that may be used inthe present reaction are, for example, xylene, toluene, benzene, mineralspirits, cyclohexane, tetrahydrofuran, diethyleneglycoldimethyl ether,etc. The reaction may also be carried out at room temperature. Onedifficulty with allowing the reaction to be carried out at roomtemperature is because of the slowness of the reaction, it requires aconsiderable amount of time to obtain an acceptable yield of percent topercent under those conditions. Thus, the reaction is preferably carriedout at a temperature range of 01 to 120 C and, more preferably, in atemperature range of to C to allow the reaction to proceed to completionin the period of 3 to 24 hours. In that reaction time, it is possible toobtain a yield of 70 percent to 80 percent of the desired product offormula (1). However, if the reaction is allowed to proceed for a longerperiod of time, such as say 48 hours and above, it is possible to obtaina more increased yield than the 80 percent level.

Further, the reaction of the compound of formula 2) with the compound offormula (3) does not require a catalyst. However, an acid catalyst or abasic catalyst may be used to allow the reaction to proceed with thedesired yield of 70 percent to 80 percent at a lower reaction time of 12hours to 14 hours. In terms of acid catalysts, there may be used a wellknown Lewis acid catalyst such as, for example, ammonium chloride, borontrifluoride, acetic acid, etc. However, an acid catalyst is notpreferred because there is the possibility that the acid catalyst mightinter-react with the amine reactant. As such, in the present reaction itis preferable to use a basic catalyst, such as potassium hydroxide orsodium hydroxide. Other preferable basic catalysts that are morepreferred in the present reaction are tertiary amines, such astributylamine, quaternary ammonium hydroxides, sodium methoxide andother such compounds. The catalyst should be present in the reactionmixture in the concentration of 0.5 to 5 weight per cent by weight ofthe reaction mixture. As an upper limit, the concentration of thecatalyst should be no more than 3 percent by weight of the reactionmixture. More preferably, the concentration of the basic catalyst shouldbe 0.5 to 1.5 percent by weight of the reaction mixture. For obviousreasons, if the catalyst concentration is below 0.5 weight per cent,then such a catalyst does not have the necessary affect on the reaction.On the other hand, if the catalyst concentration is more than 5 percentby weight, then the additional catalyst is not necessary and there isthe possibility that it might degrade the final reaction product offormula (1)- The compounds of formula (3) are well known in the art andare available and are being sold by such companies as Pennsalt ChemicalCo., Philadelphia, Pa., and Union Carbide Corporation, New York, NewYork.

The compounds of formula (2) are produced by reacting a compound of theformula,

with a compound of the formula,

Rn Zd-o-i-JI 7 where b varies from to 18, R and R are the same asdefined previously and Z is halogen. The reaction of the compounds offormulas (4) and (5) preferably take place in the presence of a platinumcatalyst. The radical Z is formula (5) may be substituted with theradicals R N or R'0, prior to or after the reaction between thecompounds of formulas (4) and (5). Preferably, this is done before thereaction of the compounds of formulas (4) and (5 to obtain a compoundwithin the scope of formula (2). A reference which illustrates thisreaction is mentioned in Eabom Organosilicon Compounds, Chap. 9 and l l,Butterworth Scientific Publications (I960). The disclosure of thesereferences are hereby incorporated into this patent application byreference. Thus, the compound of formula (5) may be taken and reactedwith a secondary amine of the formula R' NH in stoichiometricrelationship to obtain the desired product. In this reaction, there isused at least 100 percent in excess of the amine to remove the excesshydrogen chloride that is formed, such that the secondary amine acts asa hydrogen chloride acceptor so as to prevent the hydrogen chloride thatis formed from further reacting with the silane of formula (5). Otherhydrogen chloride acceptors or scavangers may be used, such astributylamine and trimethylorthoformate. If it is desired, this reactiontakes place either at room temperature or at elevated temperatures, suchas 80 to 120 C in the period of 2 to 8 hours. A catalyst is notnecessary in this aminization reaction.

On the other hand, if it is desired to substitute the halogen in formula(5) with an R'0 group, then the silane of formula (5) is reacted in astoichiometric proportion with an alcohol of the formula R'Ol-l, wherethe symbol R is as defined previously. In this reaction, the tworeactants are merely added together and heated to a temperature above 50C and, preferably, less than 150 C and, more preferably, in the range of50 to 100 C, to result in the alcoholysis product. In this reaction, acatalyst is not necessary and it is not used. The alcoholysis reactionproceeds to 75 to 90 percent to completion as does the aminizationreaction in the period of 4 to 8 hours. For more details as to thismethod, one is referred to the above-mentioned reference.

The reaction between the compounds of formulas (4) and (5) in thepresence of a platinum catalyst is an SiH platinum catalyzed olefinaddition reaction. The platinum compound catalyst can be selected fromthat group of platinum compound catalysts which are operative tocatalyze the addition of silicon-hydrogen bonds across olefinic bonds.Among the many useful catalysts for this addition reaction arechloroplatinic acid as described in U.S. Pat. No. 2,823,218 Speier etal; the reaction product of chloroplatinic acid with either an alcoholand ether or an aldehyde as described in U.S. Pat. No. 3,220,972Lamoreaux; trimethylplatinum iodide and hexamethyldiplatinum asdescribed in U.S. Pat. No. 3,313,773 Lamoreaux; the platinum olefincomplex catalyst as described in U.S. Pat. No. 3,159,601 Ashby and theplatinum cyclopropane complex catalyst described in U.S. Pat. No.3,159,662 Ashby.

The SiH-olefin addition reaction may be run at room temperature ortemperatures up to 200 C, depending upon catalyst concentration. Thecatalyst concentration can vary from 10' to 10' and, preferably, 10' to10" mole of platinum as metal to a mole of the olefiniccontainingmolecules present. For further information as to such a type ofreaction, one is referred to Journal of American Chemical Society, Vol.79, page 974 (1957), whose disclosure insofar as it relates toSil-lolefin addition reaction is hereby incorporated into the presentdisclosure by reference.

The compounds within the scope of formula (4) above are well known inthe art and are sold by such companies as Sartomer Resins Company,Philadelphia, Pennsylvania, Borden Chemical Company, Philadelphia, Pa.,Aldrich Chemical Company, Milwaukee, Wisconsin, Alcolac ChemicalCompany, Baltimore, Maryland. Quite simply, the compounds of formula (4)above are obtained by reacting an olefinic chloride of the formula,

CH =CH(CH ,CI (6),

with an acrylate of the formula,

0 R: R2 .WKO Ci- 391i where K stands for potassium and the symbols R andb are as defined previously. The above reaction takes place preferablyin an inert solvent, such as ketones, using a tertiary amine catalyst.The compounds of formulas (6) and (7) are reacted in stoichiometricproportions. This is a well known type of Williamson reaction. Acatalyst such as tertiary amine is helpful in this reaction, since thereactants react most efficiently to result in the product of formula (4)in 85 to 90 percent yields in a reaction time of 2 to 12 hours. Thisreaction may be carried out at room temperature but is preferablycarried out so as to obtain high yields in as short a period of time inthe temperature range of 80 to 150 C. In the case where b is equal to inthe compound of formula (4), it is necessary to adopt a different methodof synthesis. In that case, the reacting compounds, as well as thereaction product, may be illustrated by the following reaction:

In reaction I, R is as defined previously. With the above reaction, itis possible to obtain the product indicated in 85 percent to 90 percentyields by earring the reaction in an inert hydrocarbon solvent such asxylene, toluene, benzene, cyclohexane, etc. Preferably, the reactionconditions are such that the temperature of the reaction is maintainedbelow 50 C to obtain the desired high yield. In this reaction, acatalyst is necessary and the preferred catalyst system is a mixture ofmercuric acetate with sulfuric acid in a concentration of 0.3 to percentby weight of the two reactants.

The following examples are presented below for the purpose ofillustrating the present invention. They are not intended or should itbe inferred that they limit the scope of the invention as claimed in anyway.

EXAMPLE 1 Synthesis of a compound of the formula,

A reaction mixture containing 37 g (0.5 mole) isobutylamine and 124 g(0.5 mole) trimethoxysilylpropyl methacrylate is allowed to stir atambient temperature for two hours. A very mild exothermic reaction isevident. The temperature rises from 29 to 33 C in this interval of time.Following this, the reaction is brought to 70 C by the application ofexternal heat and held there for four hours. A VPC scan at this timeshows indeed, an adduct is formed. Upon fractionation, a product isobtained; B.P. l14/0.25 mm in about 55 percent conversion. But the yieldis substantially higher based on recovered starting materials.

EXAMPLE 2 A reaction mixture is charged with 76 g allyl chloride, 238 gsodium methacrylate, 50 g methylethyl ketone, 5 g each of triethylamineand sodium iodide and is heated to 95 100 C (under slight pressure) for2 hours. The product is then isolated and purified. A mixture of 127 g(1 mole) allyl methacrylate and onefourth mole of a 0.1M chlorolatinicacid solution in isopropanol is prepared. The reaction is heated to 80 Cwhereupon there is added dropwise 133 g triehlorosilane (1 mole). Anexothermic reaction begins. Rate of silane addition is controlled tokeep reaction pot temperature to 130 C. Upon complete silane addition,the reaction is heated to C for 2 hours. Then there is distilled theproduct trichlorosilylpropyl methacrylate which is isolated. The purityis checked by gas chromatography and structure confirmed by infrared andnuclear magnetic resonance with a yield which is above 90 percent. Then130 parts of the above silane is placed in a pot and 48 parts methanolis added dropwise at ambient temperature. Hydrogen chloride immediatelyevolves and the reaction temperature climbs slowly to about 45 C. Whenall the methanol is added, the pot is brought to reflux whereupon anadditional 24 parts is added. The reaction is kept at reflux and samplesperiodically withdrawn until the chloride level is less than 5 ppm. Thereaction is then fractionated to obtain pure To g of the above is slowlyadded 44 g N,N- dimethylethylenediamine. A mild exotherm is noted duringthe latter part of the addition. After complete addition, the reactionis heated to 90 C for 8 hours. Gas chromatography analysis indicates anadduct is present. The product is purified by fractionation and itsstructure is confirmed as,

To parts of trichlorosilylpropyl methacrylate in 1,000 parts ofanhydrous tetrahydrofuran is added slowly 134 parts dimethylamine (via agas cylinder). A very exothermic reaction occurs. An immediateprecipitate of dimethylamine hydrochloride occurs. As stirring becomesdifficult, additional solvent is added. After complete amine addition,the reaction is refluxed for 4 hours and filtered. To the supernatantliquid is then added 30 additional grams of dimethylamine. Afterrefluxing for 6 hours, a gas chromatography analysis of the reactionmixture shows a high boiling adduct is produced. Distillation of the potcontent results in the recovery of,

H CH3 whose structure is confirmed by both infrared and nuclear magneticresonance.

EXAMPLE 4 The addition of 43 g ethylenimine to 202 gdimethylmethoxysilylpropylacrylate is carried out by mixing bothmaterials together, allowing the reaction to proceed at room temperaturefor 4 hours. Then the mixture is heated to 60 C for 8 hours.Fractionation produces the desired product.

$113 H CH2 CH30- S l-CHzCH2CH20CCHzCHz-N H; CH

EXAMPLE There is added equimolar amounts of B- cyanoethylamine todiethoxymethylsilylmethacrylate and the resulting mixture is heated for8 hours at 100 C to produce the product of the structure,

The structure is confirmed by both infrared and nuclear magneticresonance.

We claim:

1. A silane of the formula,

where L is selected from the group consisting of R N and RO, R and R areselected from the-class consisting of monovalent hydrocarbon radicalsand monovalent halogenated hydrocarbon radicals, R is selected from theclass consisting of alkyl and aryl radicals of up to carbon atoms, R andR are independently selected from the class consisting of hydrogen, arylradicals, alkyl radicals,

and R OR, where R is a divalent hydrocarbon radical selected from theclass consisting of alkylene and arylene radicals of up to 10 carbonatoms, n is a whole number that varies from 1 to and a is a whole numberthat varies from 0 to 2.

2. A compound of claim 1 wherein R, R and R are methyl and n is equal to3.

3. The compound of claim 1 wherein the compound has the formula,

4. A method for producing a silane compound of the formula,

l r 152 9 :9: VQ -B:

comprising reacting a compound of the formula,

O R R with a compound of the formula,

I iiwhere L is selected from the class consisting of R N and RO, R and Rare selected from the class consisting of monovalent hydrocarbonradicals and monovalent halogenated hydrocarbon radicals, R is selectedfrom the class consisting of alkyl and aryl radicals of up to 10 carbonatoms, R and R are independently selected from the class consisting ofhydrogen, aryl radicals, alkyl radicals,

and R OR where R is a divalent hydrocarbon radical selected from theclass consisting of alkylene and arylene radicals of up to 10 carbonatoms, n is a whole number that varies from 1 to 20 and a is a wholenumber that varies from 0 to 2.

5. The method of claim 4 wherein the reaction is carried out attemperatures of 60 C.

6. The method of claim 4 wherein a basic catalyst is used.

7. The method of claim 6 wherein the basic catalyst is selected from theclass consisting of sodium hydroxide, sodium methoxide, sodium ethoxideand potassium hydroxide.

2. THESE AMINO-FUNCTIONAL SILANE COMPOUNDS MAY BE USED AS SEWAGEFLOCCULENTS.
 2. A compound of claim 1 wherein R, R1 and R2 are methyland n is equal to
 3. 3. The compound of claim 1 wherein the compound hasthe formula,
 4. A method for producing a silane compound of the formula,comprising reacting a compound of the formula, with a compound of theformula, where L is selected from the class consisting of R''2N- and R''O-, R and R1 are selected from the class consisting of monovalenthydrocarbon radicals and monovalent halogenated hydrocarbon radicals, R2is selected from the class consisting Of alkyl and aryl radicals of upto 10 carbon atoms, R3 and R4 are independently selected from the classconsisting of hydrogen, aryl radicals, alkyl radicals, and -R5OR1, whereR5 is a divalent hydrocarbon radical selected from the class consistingof alkylene and arylene radicals of up to 10 carbon atoms, n is a wholenumber that varies from 1 to 20 and a is a whole number that varies from0 to
 2. 5. The method of claim 4 wherein the reaction is carried out attemperatures of 60* - 120* C.
 6. The method of claim 4 wherein a basiccatalyst is used.
 7. The method of claim 6 wherein the basic catalyst isselected from the class consisting of sodium hydroxide, sodiummethoxide, sodium ethoxide and potassium hydroxide.